Microsoft Word 郭萌萌二校出289

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1 7 1 Vol. 7 No Journal of Food Safety and Quality Jan., 郭萌萌, 刘雪卉, 吕运开 *, 马俊琴 (, ) 摘要 : 目的,, 方法,,, - (PC) 结果 85.36%~95.47%, (RSD, n=5) 1.28%~5.64%, 1.24~2.14 ng/ml 4.15~7.12 ng/ml 结论,, 关键词 : ; ; ; ; Determination of migration of three kinds of phenolic compounds from food contact materials using magnetic dispersion extraction-high performance liquid chromatography GUO Meng-Meng, LIU Xue-Hui, LV Yun-Kai *, MA Jun-Qin (College of Chemistry and Environmental Science, Hebei University, Baoding , China) ABSTRACT: Objective To synthesize a kind of magnetic microspheres with porous surface for adsorption enrichment and highly sensitive analysis of the migration of phenols from food packaging material. Methods Carboxylated magnetic microspheres were synthesized by one pot method, and then magnetic metal-organic frameworks (MOFs) were prepared by layer self-assembly technique. The MOFs were used as adsorbent for magnetic dispersion extraction of migratory quantity of phenolic compounds from polycarbonate bottles. Results The average recoveries were in the range of 85.36%~95.47% with the RSD of 1.28%~5.64%. The limits of detection and quantitation of the proposed method were in a range of 1.24~2.14 ng/ml and 4.15~7.12 ng/ml, respectively. Conclusion The synthetic method of the magnetic MOFs is simple and feasible, and its adsorption performance is satisfactory. The extraction and detection method is simple, rapid and high enrichment factors with satisfactory precision and accuracy, and is suitable for the separation and analysis of the phenolic compounds. KEY WORDS: magnetic metal-organic frameworks; magnetic dispersion extraction; high performance liquid 基金项目 : ( ) (B ) Fund: Supported by the National Natural Science Foundation of China ( ) and Natural Science Foundation of Hebei Province (B ) * 通讯作者 :,, lvyunkai@hbu.edu.cn *Corresponding author: LV Yun-Kai, Professor, College of Chemistry and Environmental Science, Hebei University, 180 Wusi Road, Baoding , China. lvyunkai@hbu.edu.cn

2 286 7 chromatography; food contact materials; phenols 1 引言,,,,,, A (BPA),, [1],, [2,3],, ; [4] No10/2011 A 0.05 mg/kg 0.6 mg/kg [5],, [6] - [7] [3,4,8] - [9,10], ;,,, [11],,,, - [12] ( ) [3,4,9,10] [8], (MDE) [13], (MOFs), - (Fe 3 O - A ( - ), PC PC,, 2 材料与方法 2.1 材料与试剂 PC : ; A 99%, ; 2- ( ) ; 2.2 仪器与设备 Shimadzu LC-20A : SPD-20A ( ) Venusil XBP C18 ( mm, 5 m) ( ); ( ); ( ) : : ph 4.5 -, : 10 μl; : 1.0 ml/min; : ; : 278 nm 2.3 方法 Fe 3 O 4 ZIF-67 吸附剂的制备 8.1 g FeCl 3 6H 2 O 150 ml,,, 14.4 g NaAc 1.5 g, 12 h, 100 ml, h,,, Fe 3 O 4,, h [14] g Fe 3 O 4, 30 ml, 70, g CoCl 2 6H 2 O g 2-, 30 min,, 30 ml,,, ZIF-67 -, MOFs h

1, : - 3 287 2.3.2 标准工作储备液的配置 A 100 mg, 0.0001 g, 10 ml, 100 ml,, 3 100 mg/l 1.0 ml 1000 mg/l, 100 ml,, 10 mg/l ph 4.5 -, 2.3.3 样品预处理 PC 5 cm 2 cm, 2 ml/cm 2, 5, 200 ml (1:1, V:V) 40, 20 min,, 50, 10 ml, : 50 mg Fe 3 O 4 @ZIF-67 5 ml (4:1, V:V), 5 min, 2.

59, Fe 3 O 4 (111) (311) (400) (511) (440),, XRD, Fe 3 O 4 Fe 3 O 4 ZIF-67, Fe 3 O 4, ZIF-67, Fe 3 O 4 @ZIF-67 3 结果与分析 3.

3 1, : 标准工作储备液的配置 A 100 mg, g, 10 ml, 100 ml,, mg/l 1.0 ml 1000 mg/l, 100 ml,, 10 mg/l ph 4.5 -, 样品预处理 PC 5 cm 2 cm, 2 ml/cm 2, 5, 200 ml (1:1, V:V) 40, 20 min,, 50, 10 ml, : 50 mg Fe 3 O 5 ml (4:1, V:V), 5 min, 2.0 ml Fe 3 O 3 ml,, 40, 1 ml, 0.22 μm, 2 Fe 3 O 4 ZIF-67 Fe 3 O PXRD, , Fe 3 O 4 (111) (311) (400) (511) (440),, XRD, Fe 3 O 4 Fe 3 O 4 ZIF-67, Fe 3 O 4, ZIF-67, Fe 3 O 3 结果与分析 3.1 金属有机骨架复合材料的表征 Fe 3 O 4 Fe 3 O 1, Fe 3 O 4, Fe 3 O 4, ZIF-67, -,, 400 nm, 50 nm 1 MOFs Fig. 1 The TEM image of Fe 3 O 4 functionalized with carboxylic acid group (a) and Fe 3 O (b) 2 Fe 3 O 4 (a) ZIF-67(b) Fe 3 O X- Fig. 2 The powder X-ray diffraction pattern of Fe 3 O 4 (a), ZIF-67 (b) and Fe 3 O (c), Fe 3 O 3 200, 5% ; 200~400, 4% ; 400, MOFs, MOFs 3.2 磁分散萃取条件的优化吸附剂用量的选择 20 ml 40 µg/ml, mg,, 4a, 5~20 mg, 3

4 288 7 ; 20~40 mg,, 20 mg Fe 3 O 4c, 0.2 mol/l NaCl, 萃取时间的影响, 4d, A 20 min, 10 min, 15 min,,, 3.3 方法学验证 3 Fe 3 O 4 (a) Fe 3 O Fig. 3 TGA curves of Fe 3 O 4 (a) and Fe 3 O (b) 样品溶液 ph 值的选择 ph 4b, ph 2~6, ; ph,, 3,, ph 6,, [15], ph 6 ph 盐浓度的影响,, ;,, 线性方程检出限定量限 mg/l, 3, 1 0.5~10.0 mg/l, 3 (r 2 ) , (LOD, S/N=3) 1.24~2.14 ng/ml, (LOQ, S/N=10) 4.15~7.12 ng/ml 实际样品分析和加标回收率 2.3.3, MOFs, -, PC A, 5 5a 5b 5c PC PC 0.1 mg/l, A PC, 3, 6.55 g/l ( A) 4.28 g/l ( ) 2.14 g/l ( ), [4], Fig. 4 4 (a) ph(b) (c) (d) Effects of the amount of adsorbent (a), sample ph (b), the concentration of salt (c) and adsorption time (d) on the extraction efficiencies.

5 1, : , A, mg/l 5,,, %~95.47%, (RSD) 1.28%~5.64%, PC (1 2 3 A) Fig. 5 Chromatograms of bisphenol A, phenol and resorcinol obtained from blank extracting solution of PC bottle (a), blank extracting solution after MDE (b) and extracting solution of PC sample spiked with concentration (0.1 mg/l) (c). Table 1 表 1 酚类物质的标准曲线检测结果 (n=5) Detection results standard curves of phenols (n=5) r 2 LOD ( g/l) LOQ ( g/l) A Y= C Y= C Y= C Table 2 表 2 实际样品测定与加标回收率实验结果 (n=5) Results of sample tests and spiked recovery of phenols (n=5) ( g/l) ( g/l) ( g/l) (%) RSD (%) A

290 7 4 结论 - Fe 3 O 4 @ZIF-67,, MOFs, - PC A,, 参考文献 [1] Sonnensehein C, Soto AM. An updated review of environmental estrogen and androgen mimics and antagonists [J].

[3] Ma XX, Wang JT, Wu QH, et al. Graphene reinforced hollow fiber liquid-phase microextraction combined with HPLC for the determination of bisphenol A and 4-tert-butylphenol in bottled juice [J].

6 结论 - Fe 3 O MOFs, - PC A,, 参考文献 [1] Sonnensehein C, Soto AM. An updated review of environmental estrogen and androgen mimics and antagonists [J]. J Steroid Biochem, 1998, 5(l-6): [2] Yang MH, Ryu JH, Jeon R, et al. Effects of bisphenol A on breast cancer and its risk factors [J]. Arch Toxicol, 2009, 83(3): [3] Ma XX, Wang JT, Wu QH, et al. Graphene reinforced hollow fiber liquid-phase microextraction combined with HPLC for the determination of bisphenol A and 4-tert-butylphenol in bottled juice [J]. Food Anal Methods, 2014, 7(7): [4] Nerin C, Philo MR, Salafranca J, et al. Determination of bisphenol-type contaminants from food packaging materials in aqueous foods by solid-phase microextraction-high-performance liquid chromatography [J]. J Chromatogr A, 2002, 963(1 2): [5] Commission Regulation (EU) No 10/2011 of 14 January 2011 on plastic materials and articles intended to come into contact with food [EB/OL]. [6] Wu X, Wang L, Ma W, et al. A simple, sensitive, rapid and specific detection method for bisphenol A based on fluorescence polarization immunoassay [J]. Immunol Invest, 2012, 41(1): [7] Lopez-Cervantes J, Paseiro-Losada P. Determination of bisphenol A in, and its migration from, PVC stretch film used for food packaging [J]. Food Addit Contam, 2003, 20(6): [8] Watabe Y, Kondo T, Morita M, et al. Determination of bisphenol A in environmental water at ultra- low level by HPLC with an effective on- line pretreatment device [J]. J Chromatogr A, 2004, 1032(1 2): [9] Gallart-Ayala H, Nunez O, Lucci P. Recent advances in LC-MS analysis of food-packaging contaminants [J]. TrAC-Trend Anal Chem, 2013, 42: [10] Shao B, Han H, Hu J, et al. Determination of alkylphenol and bisphenol A in beverages using liquid chromatography/ electrospray ionization tandem mass spectrometry [J]. Anal Chim Acta, 2005, 530: [11] Yu F, Pan XJ, Wang B, et al. Determination of phenols in surface water of dianchi lake by solid extraction -hydroxyle derivatization-gc/ms [J]. Environ Chem, 2010, 29(4): [12] Jian H, Fang Y, Fu Y, et al. Studies on the extraction of phenol in wastewater [J]. J Hazard Mater, 2003, 101(2): [13] Lv YK, Zhao CX, Li P, et al. Preparation of doxycycline-imprinted magnetic microspheres by inverseemulsion suspension polymerization for magnetic dispersion extraction of tetracyclines from milk samples [J]. J Sep Sci, 2013, 36(16): [14] Zheng J, Cheng C, Fang W, et al. Surfactant-free synthesis of a Fe3O4@ZIF-8 core shell heterostructure for adsorption of methylene blue [J]. Crystengcomm, 2014, 16(19): [15] Zhou Q, Gao Y, Xie G. Determination of bisphenol A, 4-n-nonylphenol, and 4-tert-octylphenol by temperaturecontrolled ionic liquid dispersive liquid-phase microextraction combined with high performance liquid chromatographyfluorescence detector [J]. Talanta, 2011, 85(3): 作者简介 ( 责任编辑 : 金延秋 ) 郭萌萌, 硕士, 主要研究方向为食品安全分析 gmm580231@163.com 吕运开, 教授, 主要研究方向为食品安全分析 lvyunkai@hbu.edu

g ml 10% ph 色谱条件 kinetex C μm 100 A 4. 6 mm 150 mm 25 5 μl A B 10 mmol /L ml /min

g ml 10% ph 色谱条件 kinetex C μm 100 A 4. 6 mm 150 mm 25 5 μl A B 10 mmol /L ml /min 25 4 2013 8 监测技术 5 1 2 1 ( 1. 江苏省疾病预防控制中心, 江苏南京 210009; 2. 南京医科大学第二附属医院, 江苏南京 210029) 5 Phenomenex kinetex C 18 2. 6 μm 4. 6 mm 150 mm 10 mmol /L ph 2. 5 + 60 40 DAD 280 nm 5 20. 0 mg /L ~ 100 mg /L 0.

Microsoft Word 郭萌萌二校 出289

Microsoft Word 郭萌萌二校出289